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A penta-coordinated dinuclear Zn(II) complex, [Zn2(L)(μ-PhCOO)(EtOH)] (1), and a hexa-coordinate tetranuclear Cd(II) complex, [{Cd2(L)(EtOH)(η-OAc)}2]·2CH2Cl2 (2), have been synthesized by reactions of a single-armed salamo-based ligand, H3L, and two kinds of transition metal salts, (Zn(NO3)2·6H2O and Cd(OAc)2·2H2O), respectively. Complexes 1 and 2 have been characterized by elemental analyses, single crystal X-ray diffraction, IR spectra and UV-Vis spectra. Complex 1 is composed of a totally deprotonated ligand (L)3- moiety, two Zn(II) ions, one μ-PhCOO- counter-anion and one coordinated ethanol molecule. The (L)3- unit packages two Zn(II) ions, the μ-PhCOO- counter-anion bridges two adjacent Zn(II) ions and one ethanol molecule coordinates with the Zn2 ion, so that both Zn(II) ions are penta-coordinated with slightly distorted trigonal bipyramidal configurations, and the τ5 values of Zn1 and Zn2 are 0.86 and 0.65, respectively. Complex 2 consists of two discrete and similar electroneutral tetra-nuclear units, 2 A and 2B, and two crystallized dichloromethane molecules. Each unit has a symmetric structure that is made up of two completely deprotonated ligand (L)3- moieties, four Cd(II) ions, two η-OAc- counter-anions and two coordinated ethanol molecules. Fluorescence properties and Hirshfeld surfaces analyses have been studied as well. [ABSTRACT FROM AUTHOR]

The coordination behaviors of asymmetric quinoline-decorated half-salamo-type ligand HL1 with Cu(NO3)2·3H2O and Cu(OAc)2·H2O were studied. Two Cu(II) complexes, [Cu(L1)(NO3)]·CH3CH2OH (1) and [Cu2(L2)2] (2), were isolated and characterized by X-ray crystallography, FTIR, UV–vis, and fluorescence spectroscopies. Structural analyses showed that 1 is a mononuclear species, whereas 2 is a binuclear entity. Spontaneous cleavage along the oxime N-O bond close to quinoline ring of the ligand HL1 occurred upon reaction with Cu(OAc)2·H2O, yielding an unexpected complex 2. Moreover, DFT theoretical calculations and Hirshfeld surfaces analyses of the ligand HL1 and its corresponding Cu(II) complexes were investigated in detail. [ABSTRACT FROM AUTHOR]

A relatively rigid acyclic salamo-type ligand H2L and its square planar Cu(II) complex, [Cu(L)]·CH3OH, were synthesized and characterized by X-ray crystallography, as well as Fourier-transform infrared spectra, UV–Vis spectra, Hirshfeld surface analyses and DFT calculations. The ligand crystallizes in monoclinic space group P 21/c and has pairs of intramolecular hydrogen bonds between the oxime nitrogen atoms and the hydroxyl groups. The Cu(II) complex crystallizes in the monoclinic space group P 21/c. The Cu(II) ion is located in the N2O2 cavity of the fully deprotonated salamo-type ligand (L)2− unit, thus forming a four-coordinate distorted square planar geometry. At the same time, a belt-like, 2-D supramolecular structure is formed by the interaction of intermolecular hydrogen bonds, and the intermolecular interaction force is quantitatively analyzed by Hirshfeld surfaces. Significantly, fluorescence properties of the ligand and its Cu(II) complex were also studied. The coordination ratio of the Cu(II) complex was proved by UV–Vis and fluorescence titration experiments. [ABSTRACT FROM AUTHOR]

Two novel homomultinuclear complexes [Co6(L)2(μ‐OAc)4]·2CHCl3·CH3COCH3 (1) and [Ni2(L)(H2O)2(Py)2]·2CHCl3 (2) with a newly designed rigid bis(salamo)‐type tetraoxime ligand (H4L) were synthesized and characterized by elemental analyses, Fourier transform infrared (FT‐IR) spectra, UV–Vis absorption spectra, and X‐ray single‐crystal diffractions. Complex 1 is a novel triple‐decker symmetrical six‐core cluster structure with twofold axis and inversion center. The Co(II) atoms were sandwiched between the bis(salamo)‐type ligands and possess two different geometries of distorted tetragonal pyramid and octahedron, respectively. Complex 2 possesses a dinuclear structure and the Ni(II) atoms are located in the N2O2 cavities of the ligand, and axial coordination atoms come from the coordinated water and pyridine molecules. Both Ni(II) atoms adopt distorted octahedral geometries. The interactions were quantitatively determined by Hirshfeld surfaces analyses of complexes 1 and 2. The coordination ratios were determined by studying the fluorescence properties of complexes 1 and 2. The results of fluorescence titration experiment show that the metals to ligand binding ratios are 6:2 and 2:1 for complexes 1 and 2, respectively. [ABSTRACT FROM AUTHOR]

Two dinuclear Ni (II) and Zn (II) salamo‐type complexes, [Ni2(L)(μ‐OAc)(MeOH)]·2CHCl3 (1) and [{Zn2(L)(μ‐OMe)}3]·3CHCl3·MeOH (2), have been successfully synthesized by wet‐chemical method and characterized by elemental analyses, IR spectra, UV–Vis spectra and single crystal X‐ray diffraction. Complex 1 consists of two closely related dinuclear units 1A and 1B, and complex 2 consists of three closely related dinuclear units 2A, 2B and 2C. The five units are unique example of crystallographically independent but chemically identical molecules. The Ni (II) atoms of complex 1 are located in the N2O4 coordination cavities, possessing six‐coordinated distorted octahedral geometries, but all Zn (II) atoms in complex 2 are located in the N2O3 coordination cavities, possessing five‐coordinated distorted square‐pyramid and triangular bipyramid geometries, the geometries about the Zn (II) atoms (Zn3 and Zn6) that obtain in 2B and 2C where τ5 is very close to 0.500, which is τ5Zn3 = 0.5006 and τ5Zn6 = 0.4941, respectively. The interactions were quantitatively determined by Hirshfeld surfaces analyses. Significantly, fluorescence properties were also investigated. [ABSTRACT FROM AUTHOR]

A family of rare structurally different homometal multinuclear CuII bis(salamo)‐based complexes, [Cu4(L)2(MeOH)2](ClO4)2·2MeOH (1), [Cu4(L)2(EtOH)2](NO3)2·2EtOH (2) and [Cu2(HL)(EtOH)Br2]·CHCl3 (3), has been successfully synthesized by the reactions of cupric salts with a bis(salamo)‐based multidentate chelate ligand (H3L). The salamo‐based ligand [R‐CH=N—O—(CH2)n—O—N=CH—R] is a new type of salen‐based analog. Complexes (1) and (2) are isostructural structures, and crystallize in monoclinic space group P21/n with centrosymmetric spiral structures, where the main structures contain two fully deprotonated ligand (L)3− units, a charged tetranuclear CuII folding center and two coordinated solvent molecules. Complex (3) crystallizes in monoclinic space group Cc and consists of two CuII cations, one incompletely deprotonated ligand (HL)2− unit and one coordinated ethanol molecule, and forms a novel homo‐binuclear CuII complex structure due to Br− counter anions. Complexes (1)–(3) have zero‐dimensional cluster‐based structures and are further assembled into three‐dimensional frameworks via intermolecular interactions. Because of the different solvents and counter anions which have a significant influence on the structures of complexes (1)–(3), the interactions were quantitatively evaluated by Hirshfeld surfaces analyses. Complexes (1)–(3) have been characterized by elemental analyses, IR spectra, UV–vis spectra and X‐ray crystallography analyses. In addition, fluorescence properties are evaluated and DFT calculations are performed. [ABSTRACT FROM AUTHOR]

Using symmetrical bis (salamo)‐type tetraoxime ligand H3L and Cu (ClO4)2·6H2O in different solvent systems, two unusual homomultinuclear Cu (II) complexes, [Cu4(L)2(CH3CH2OH)2](ClO4)2·2H2O (1) and [Cu2(L)]n (ClO4)n·nCH3CN (2), were synthesized and characterized by single‐crystal X‐ray diffraction analyses, elemental analyses, infrared (IR), ultraviolet–visible (UV–Vis) spectroscopy, Hirshfeld surfaces analyses, and density functional theory (DFT) calculations. Complex 1 includes [Cu4(L)2(CH3CH2OH)2]2+ ion, two ClO4− counter anions, two coordinated ethanol molecules and two aquatic dissociative molecules, the two deprotonated ligand (L)3− units package around four Cu (II) ions yield a centrosymmetric helical molecules with a charged linear folding center, while complex 2 forms a 1‐D linear topology structure and is only the substitution of chloroform in the solvent system of complex 1 with acetonitrile. Coordination mode of complex 2 is widely different from that of complex 1. In the Cu (II) ions of complex 1, there are two coordination modes of Cu (II) ions, the hexa‐coordinated distorted octahedral structure and the penta‐coordinated distorted tetragonal pyramid structure, but complex 2 only has almost perfect tetragonal pyramid geometry. Fluorescence properties of H3L and its complexes 1 and 2 have also been explored. [ABSTRACT FROM AUTHOR]

Two new tetranuclear NiII complexes, [Ni4(L1)2(N3)4(MeOH)2]·CH3COCH3(1) and [Ni4(L2)2(N3)4(MeOH)2]·4CH3COCH3(2), were synthesized using NiCl2·6H2O, NaN3, and asymmetric salamo‐based ligands H2L1 and H2L2, respectively. The structural characterization was made by elemental analyses, infrared (IR) and ultraviolet‐visible (UV‐vis) spectra, and X‐ray diffraction analyses. The results of X‐ray diffraction analyses show that the NiII atoms in complexes 1 and 2 are distorted octahedral geometries. Interestingly, the degree of distortion of the ligands in complexes 1 and 2 is different, which indicates that the interaction of NiII ions on different ligands is different. Meanwhile, the investigation of molecular packing by employing the Hirshfeld surface analysis exhibits that the percentages of C–H/H–C, O–H/H–O, and H–H/H–H contacts of the complex 1 (or 2) are calculated to be 17.7%, 7.9%, and 53.7% (or 18.8%, 13.8%, and 52.5%), respectively, where the H–H/H–H contacts have the characteristics of strong contacts whereas the O–H/H–O hydrogen bonds are considerably weak, and the studies on fluorescence properties further confirm the NiII atoms have different binding abilities to the different ligands. [ABSTRACT FROM AUTHOR]

Two hetero‐bimetallic [Zn(II)2M(II)] (M = Ca and Sr) complexes [Zn2Ca(L)(OAc)2] (1) and [Zn2Sr(L)(OAc)2] (2) with a novel asymmetrical bis(salamo)‐type tetraoxime ligand (H5L) were designed and synthesized, and characterized by elemental analyses, FT‐IR spectra, UV–vis absorption spectra, Density Functional Theory (DFT) calculation, Hirshfeld surface analyses and X‐ray single crystal diffractions. Compared with the symmetric bis(salamo)‐type ligands, the ligand H5L and its [Zn(II)2M(II)] (M = Ca and Sr) asymmetrical bis(salamo)‐type complexes synthesized for the first time in this paper have more novel structures and better properties. The results of ultraviolet titration show that the coordination ratio of ligand, alkaline earth metal and transition metal is 1:1:2. Complexes 1 and 2 have good luminescent properties and obvious antimicrobial activities. [ABSTRACT FROM AUTHOR]

An unexpected trinuclear Co(II) complex, [Co3(L2)2(μ-OAc)2(CH3OH)2]·2CH3OH (H2L2 = 4,4′-dibromo-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol) constructed from a half-Salamo-based ligand (HL1 = 2-[O-(1-ethyloxyamide)]oxime-4-bromophenol) and Co(OAc)2·4H2O, has been synthesized and characterized by elemental analyses, infrared spectra (IR), UV-Vis spectra, X-ray crystallography and Hirshfeld surface analysis. The Co(II) complex contains three Co(II) atoms, two completely deprotonated (L2)2− units, two bridged acetate molecules, two coordinated methanol molecules and two crystalline methanol molecules, and finally, a three-dimensional supramolecular structure with infinite extension was formed. Interestingly, during the formation of the Co(II) complex, the ligand changed from half-Salamo-like to a symmetrical single Salamo-like ligand due to the bonding interactions of the molecules. In addition, the antimicrobial activities of HL1 and its Co(II) complex were also investigated. [ABSTRACT FROM AUTHOR]

A new homo-trinuclear Ni(II) half-salamo-based complex [Ni3(L)2(μ-OAc)2(OAc)2(CH3OH)2]·2CH3OH was synthesized via the reaction of a tridentate ligand HL (2-[O-(1-ethyloxyamide)]oxime-4-bromophenol) and Ni(OAc)2·4H2O, and characterized using elemental analyses, IR spectra, UV-Vis absorption spectra, X-ray crystallography, and Hirshfeld analysis. Interestingly, single-crystal X-ray analysis showed that the two acetate molecules were bonded simultaneously with the Ni(II) atoms by mono-dentate chelating and bidentate bridging coordination modes, respectively, and the resulting hexa-coordinate geometries were ultimately formed. Furthermore, the Hirshfeld analysis of the complex was studied. Compared with HL, the complex fluorescence intensity was significantly lowered, indicating that the Ni(II) ions have fluorescence quenching characteristics. [ABSTRACT FROM AUTHOR]

The newly designed butterfly-shaped hetero-tetranuclear CuII-NaI coordination compound, [Cu3(HL)2Na]∙Pic (Pic− is abbreviation of picrate) (1) which is derived from a naphthalenediol-based bis(Salamo)-type chelating ligand H4L have been synthesized and characterized by elemental analyses, UV-vis spectra, IR spectra analysis, and Hirshfeld surface analysis. X-ray crystallographic analyses revealed that the coordination compound 1 is a novel hetero-tetranuclear CuII-NaI bis(Salamo)-type coordination compound and it differs from heterotrinuclear CuII-NaI bis(Salamo)-type coordination compound reported earlier. The Cu1 and Cu3 atoms are tetra-coordinated with geometries of distorted square pyramid, while Cu2 atom are hexa-coordinated with the geometry of a distorted octahedron. The NaI atom is octa-coordinated with the geometry of a distorted hexagonal bipyramid. Furthermore, the supramolecular structure and Hirshfeld surface analyses have been discussed in detail. [ABSTRACT FROM AUTHOR]

• A quinoline-including half-salamo like N 3 O-donor ligand was synthesized. • Differently structural Cu(II) and Ni(II) complexes were synthesized and structurally characterized. • The intermolecular interactions were quantitatively analyzed by hirshfeld surfaces and 2D fingerprint plots. A half-salamo like N 3 O-donor ligand HL was synthesized and used for the construction of Cu(II) and Ni(II) complexes, namely as [Cu(L)(NO 3)] (1) & [Ni 2 (L) 2 (NO 3) 2 ]·2H 2 O (2). The constructed complexes were structurally characterized by X‐ray crystallography technique. The results revealed that the complex 1 is the most common mononuclear species, in which Cu(II) ion is penta-coordinate with twisted square pyramid configuration. Unlike complex 1, the central Ni(II) ions of dinuclear complex 2 are hexa-coordinate possessing slightly distorted octahedron. The final supramolecular structures of the two complexes are stabilized and expanded by noncovalent interactions. In addition, spectral characteristics of the title complexes were examined. The frontier molecular orbitals as well as energy gaps of the complexes were explored by density functional theory calculation. The primary aspects of the ultraviolet absorption spectra were interpreted using time-dependent density functional theory computation. Thorough analysis of the Hirshfeld surfaces quantifies the interactions involved in the crystal structures of the Cu(II) and Ni(II) complexes. Two differently structural metal(II) complexes [Cu(L)(NO 3)] (1) and [Ni 2 (L) 2 (NO 3) 2 ]·2H 2 O (2) containing a half-salamo like N 3 O-donor ligand were successfully synthesized and characterized. The spectral properties of the two complexes were studied. Moreover, the frontier molecular orbitals as well as energy gaps of the complexes were explored by DFT calculation. The Hirshfeld surfaces analyses and 2D fingerprint plots were performed to quantify the interactions involved in the crystal structures of the two complexes. [Display omitted] [ABSTRACT FROM AUTHOR]

• A quinoline-appended acylhydrazone H 2 L was designed and prepared. • The Zn(II) acylhydrazone complex [Zn(HL) 2 ]·H 2 O was prepared and elucidated tructurally. • The ligand HL and its Zn(II) complex showed unique luminescent mechanochromism. • The self-assembly process and weak intermolecular forces of complexes were explained. In the work, a quinoline-appended acylhydrazone H 2 L was designed and prepared via a Schiff base condensation reaction of quinoline-2-formaldehyde and salicylhydrazide. Further, a new zinc(II) complex, [Zn(HL) 2 ]·H 2 O was synthesized by the reacting of the ligand H 2 L and Zn(NO 3) 2 ·6H 2 O in dichloromethane/ethanol solution. The ligand and its Zn(II) complex were elucidated via UV–Vis, FT-IR, DFT calculation, Hirshfeld surfaces, MEP & IRI analyses, and X-ray single-crystal diffractions. The results of Hershfield surface analysis showed that there are obvious hydrogen bond interactions and C H···π mutual effect in the Zn(II) complex. In addition, solid-state photoluminescence properties indicated that H 2 L and its Zn(II) complex represent uncommon luminescent mechanochromism tuned via intermolecular hydrogen bonds. A quinoline-appended acylhydrazone ligand H 2 L and its Zn(II) complex [Zn(HL) 2 ]·H 2 O, were prepared and elucidated structurally. The results of Hershfield surface analysis showed that there are obvious hydrogen bond interactions and C H···π mutual effect in the Zn(II) complex. In addition, solid-state photoluminescence properties indicated that H 2 L and its Zn(II) complex represent uncommon luminescent mechanochromism tuned via intermolecular hydrogen bonds. [Display omitted] [ABSTRACT FROM AUTHOR]

• The quinoline-decorated N 3 O-donor half-salamo type ligand HL was designed and synthesized. • Two novel Co(Ⅱ) complexes [Co(L)Cl] (1) and [Co(L)(NCS)] (2) were obtained by the reaction of HL with different Co(Ⅱ) salts. • Quantitative analyses of intermolecular interactions in the crystalline structures were performed by Hirshfeld surfaces analysis. Self-assembly through a quinoline-decorated N 3 O donor half-salamo-type tetradentate ligand HL and coordinative preference of Co(II) ion, two novel Co(II) complexes [Co(L)Cl] (1) and [Co(L)(NCS)] (2) were synthesized and characterized. X-ray crystallography revealed that both complexes 1 and 2 have similar mononuclear structure, in which the five-coordinated Co(II) atoms are not only surrounded by the N 3 O cavity of the deprotonated ligand (L)− unit, but also coordinated with different Cl− and NCS− anions. For the involvement of different anions, the crystal structures of the two complexes exhibit intermolecular C H···Cl and C H···S hydrogen interactions in building supramolecular assemblies, respectively. The two complexes are stabilized by C H···O, C H···N, C H···C, C H···S bonds and C H···π, π···π interactions. The spectral properties of the complexes were investigated through UV–Vis and fluorescence spectroscopy. In addition, the detailed analyses of Hirshfeld surfaces and fingerprint plots provide the basis of the intermolecular interactions in building crystal blocks. Two novel Co(II) complexes, [Co(L)Cl] (1) and [Co(L)(NCS)] (2) with a quinoline-decorated half-salamo type ligand HL were synthesized and characterized structurally. In addition, spectroscopic properties, DFT calculations and Hirshfeld surfaces analyses of HL and its two Co(II) complexes were investigated in detail. [Display omitted] [ABSTRACT FROM AUTHOR]

• Complexes 1 and 2 were successfully prepared and characterized structurally. • Complex 2 is not obtained from H 3 L but from a new ligand H 2 L1. • Theoretical calculations and fluorescence properties were investigated in detail. Two unusual bis(salamo)-based Co(II) complexes, [Co 2 (L)(OMe)]·2MeOH (1) and [Co 4 (L1) 4 (MeOH) 4 ] (2) were designed and successfully prepared, and characterized structurally. The crystal structure analysis showed that complex 1 is composed of one fully deprotonated ligand (L)3− moity, two divalent Co(II) atoms and one bridge-coordinated methanol molecule, while complex 2 is an asymmetric homotetranuclear structure made up of four Co(II) atoms, four fully deprotonated (L1)2− units and four coordinated methanol molecules. It is noteworthy that the reaction of cobalt(II) nitrate with H 3 L produces complex 2. This complex is not obtained from the original ligand H 3 L but from a new ligand H 2 L1. Therefore, the phenomenon can be used to prepare metal(II/III) complexes with excellent structure. The molecular frontier orbitals HOMO and LUMO of H 3 L and complexes 1 and 2 were analyzed by DFT calculations, and the results showed that the energy gaps of the complexes were reduced due to the combination of the orbitals compared to the ligand. The reaction sites of H 3 L with Co(II) atoms were analyzed by ESP studies, and the results showed that the crystal structures of the complexes are consistent with the theoretical predictions. Hirshfeld surface analyses indicated the different interactions in the complexes, and revealed that the main contributions to the crystal stacking were from H H, C H and H O interactions. The interactions in the complexes were further explored by IRI research, the results exhibited that there are abundant interactions in complexes 1 and 2 , which are important for their construction of supramolecules. The fluorescence strengths of complexes 1 and 2 are significantly lower compared to H 3 L, which can be attributed to the ligand to metal charge transition (LMCT). [ABSTRACT FROM AUTHOR]

[Display omitted] Three new Co(II) complexes containing half-salamo type ligand HL viz. [Co(L)Cl] (1), [Co(L)(NO 3)] (2) and [Co(L)(NCS)] (3) were synthesized and characterized by single crystal X-ray diffraction. The results showed that the central Co(II) atoms in mononuclear complexes 1 – 3 are all located in the N 3 O cavity of the deprotonated ligand (L)− unit, while coordinated with different counteranions. The presence of counteranions in complexes 1 – 3 are Cl−, NO 3 − and NCS−, respectively. The spectral properties of these complexes were investigated in detail. In addition, the structural descriptions were corroborated with theoretical calculations. The Hirshfeld surface analysis combined with 2D fingerprint plots revealed the short-range intermolecular interactions of these complexes. [ABSTRACT FROM AUTHOR]

Graphical abstract Homo-trinuclear [Zn 3 (L)(μ 2 -OAc) 2 (H 2 O)] . CH 2 Cl 2 (1) and hetero-pentanuclear [Zn 4 (L) 2 Eu(NO 3) 3 (H 2 O)] (2) and [Zn 4 (L) 2 Nd(NO 3) 3 (H 2 O)]·CH 3 CH 2 OH (3) complexes containing a coumarin-skeleton bis(salamo)-like ligand H 4 L, were successfully prepared and structurally characterized. Hirshfeld surfaces analysis and luminescences were investigated in detail. Highlights • Trinuclear ZnII (1) and pentanuclear ZnII-LnIII (Ln = Eu (2) and Nd (3)) complexes were synthesized. • The structures of complexes 1 – 3 are reported. • Hirshfeld surface and luminescences of complexes 1 – 3 were investigated. Abstract Homo-trinuclear [Zn 3 (L)(μ 2 -OAc) 2 (H 2 O)] . CH 2 Cl 2 (1) and hetero-pentanuclear [Zn 4 (L) 2 Eu(NO 3) 3 (H 2 O)] (2) and [Zn 4 (L) 2 Nd(NO 3) 3 (H 2 O)]·CH 3 CH 2 OH (3) complexes containing a coumarin-skeleton bis(salamo) ligand H 4 L, were successfully prepared and characterized via the means of elemental analyses, single crystal X-ray crystallography, FT-IR, UV–Vis absorption spectroscopy and Hirshfeld surfaces analyses. Complex 1 is a 1:3 ((L)4−:ZnII) structure, and complexes 2 and 3 are 2:4:1 ((L)4−:ZnII:LnIII) structure. All ZnII atoms in complexes 1 – 3 occupied the N 2 O 2 sites are five-coordinated with geometries of slightly distorted tetragonal pyramid and trigonal bipyramid. Rare earth metal (EuIII and NdIII) atoms are both coordinated with phenolic oxygen atoms, and eight-coordinated with the square antiprism geometries in complexes 2 and 3. Water molecules as coordinating solvents participate in the coordination. Supra-molecular structures are built by C H ... π and hydrogen bonding interactions in complexes 1 – 3. Moreover, Hirshfeld surfaces analyses of complexes 1 – 3 were also analysed in detail. Most important of all, luminescences of complexes 1 – 3 were discussed. [ABSTRACT FROM AUTHOR]

wo unusual Cu(II) complexes [{Cu(L 1 )} 2 ] (1) and [Cu 2 (L 2 )] (2), with an asymmetric salamo-type bisoxime ligand H 2 L 1 were synthesized and characterized by elemental analyses, UV–Vis, fluorescent spectra, Hirshfeld surface analyses and single-crystal X-ray diffraction analyses. For the complex 1 , two Cu(II) ions are penta-coordinate by N 2 O 2 donor atoms from the (L 1 ) 2− unit and one bridged phenol oxygen atom from another (L 1 ) 2− unit. Complex 1 does not have intermolecular hydrogen bonds, formed an isolated zero dimensional structure. Meanwhile, for the complex 2 , an unexpected ligand H 4 L 2 was synthesized by aldol condensation reaction of H 2 L 1 and acetone upon coordination, then the new ligand and Cu(II) ions combined, formed a highly symmetrical structure, and two Cu(II) ions of the complex 2 have tetra-coordinate environment. With the help of intermolecular hydrogen bonding C H⋯O interactions, a self-assembled infinite 1D supramolecular structure was formed. Meanwhile, the photophysical spectra and Hirshfeld surface analyses of the complexes 1 and 2 were also measured and discussed. [ABSTRACT FROM AUTHOR]

• Two trinuclear Co(II) and Ni(II) complexes with a unsymmetrically salamo type ligand were synthesized and characterized structurally. • Two terminal Co(II) atoms of complex 1 possess penta-coordinated trigonal bipyramid geometries, the central Co(II) atom exhibits a hexa-coordinated octahedral geometry, while all three Ni(II) atoms of complex 2 have hexa-coordinated octahedral geometries. • Molecular electrostatic potential analysis, hirshfeld surface analysis, and interaction region indicator analysis of complexes 1 and 2 were investigated. Two trinuclear Co(II) and Ni(II) complexes, [{Co 3 (L) 2 (μ -OAc) 2 } 2 ]·3CH 2 Cl 2 (1) and [Ni 3 (L) 2 (μ -OAc) 2 (EtOH) 2 ]·2EtOH (2) have been successfully obtained by a new nonsymmetrical salamo type ligand H 2 L with Co(OAc) 2 ·4H 2 O and Ni(OAc) 2 ·6H 2 O, respectively. Single crystal X-ray diffraction analysis revealed that complex 1 is an unsymmetric trinuclear structure, two tetradentate N 2 O 2 -donor ligand (L)2- units are coordinated to three Co(II) atoms where two terminal Co(II) atoms are penta-coordinated lateral twisting trigonal bipyramidal geometries but central Co(II) atom is hexa-coordinated lateral twisting octahedral configuration. Complex 2 is a centrosymmetrical trinuclear structure, all of the three Ni(II) atoms are hexa-coordinated lateral twisting octahedral configurations. In addition, complexes 1 and 2 have been characterized by physicochemical and spectroscopic methods. Molecular electrostatic potential analysis revealed that the phenolic oxygen atoms in the ligand H 2 L have nucleophilic reactions with Co(II) and Ni(II) atoms to form chemical bonds. Hirshfeld surfaces analyses showed that H···H/H···H interactions are the predominant, indicating the presence of great amount hydrogen bonds in complexes 1 and 2. IRI analyses indicated the presence of weak hydrogen bonding interactions that made complexes 1 and 2 more stable. Two trinuclear Co(II) and Ni(II) nonsymmetrically salamo type complexes, [{Co 3 (L) 2 (μ -OAc) 2 } 2 ]·3CH 2 Cl 2 (1) and [Ni 3 (L) 2 (μ -OAc) 2 (EtOH) 2 ]·2EtOH (2) have been successfully synthesized and characterized structurally. Molecular electrostatic potential analysis, interaction region indicator analysis, Hirshfeld surfaces analyses, DFT calculations and fluorescent properties of the Co(Ⅱ) and Ni(Ⅱ) complexes were also studied. [Display omitted] [ABSTRACT FROM AUTHOR]

Two novel complexes [Cu(L)(OAc)]·CH 3 OH (1) and [Ni(L)(OAc)] (2) formed with a quinolone-modified half-salamo-like ligand (HL) were successfully synthesized and characterized structurally. In addition, Fluorescence properties, DFT theoretical calculations and Hirshfeld surfaces analyses of the ligand HL and its corresponding complexes were also investigated. [Display omitted] • The introduction of quinoline into half-salamo-like ligand HL has been developed triumphantly. • Two novel complexes [Cu(L)(OAc)]·CH 3 OH (1) and [Ni(L)(OAc)] (2) were synthesized and ascertained structurally. • Fluorescence properties, DFT theoretical calculation and Hirshfeld surfaces analyses were investigated. Two novel Cu(II) and Ni(II) complexes, [Cu(L)(OAc)]·CH 3 OH (1) and [Ni(L)(OAc)] (2) formed with a newly designed quinolone-modified half-salamo-like ligand (HL) were successfully obtained. Elemental analyses, infrared spectra and UV–visible absorption spectra were employed triumphantly to characterize the complexes 1 and 2. X-ray single-crystal diffraction analysis results indicated that the complex 1 is composed of a fully deprotonated ligand (L)- unit, one Cu(II) atom and one monodentate coordinated acetate ion. For the complex 1 , the central Cu(II) atom is five coordinated adopting a slightly distorted triangular biconical geometry, while the complex 2 has two independent structural units (molecules A and B), which shows chemically identical but crystallographically independent. The central Ni(II) atom is six coordinated possessing a distorted octahedral configuration. In addition, Fluorescence properties, DFT theoretical calculations and Hirshfeld surfaces analyses of the ligand HL and its corresponding complexes 1 and 2 were also investigated in detail. [ABSTRACT FROM AUTHOR]

Two unusual heterobimetallic [CuII 4 LnIII 2 ] complexes were constructed from a N 2 O 2 - and O 6 -donor bis(salamo)-based ligand (H 4 L), and characterized structurally. The intermolecular interactions were quantitatively analyzed by Hirshfeld surfaces, as well as, fluorescence properties have also been studied. [Display omitted] • Two structurally novel heterobimetallic hexanuclear [CuII 4 LnIII 2 ] complexes were prepared using a designed N 2 O 2 - and O 6 -donor bis(salamo)-based ligand. • The different natures of three-compartmental H 4 L lead to the site‐selective introduction of two various metalII/III atoms. • Quantitative analyses of intermolecular interactions were evaluated by Hirshfeld surfaces analyses. • The fluorescence properties were further discussed. Two unusual heterobimetallic [CuII 4 LnIII 2 ] complexes, [{Cu 4 (L) 2 La 2 (ƞ 2-NO 3) 6 (EtOH)}]·2Me 2 CO (1) and [{Cu 4 (L) 2 Ce 2 (ƞ 2-NO 3) 6 (EtOH)} 2 ]·4Me 2 CO·MeOH (2) were constructed from a N 2 O 2 - and O 6 -donor bis(salamo)-based ligand (H 4 L). The structures were characterized by physical chemistry and spectroscopy methods. The two complexes 1 and 2 have similar structures, two heterotrinuclear parts with the same structure are linked by the coordination between one CuII atom and oxime-type oxygen atoms to obtain the heterohexanuclear complexes 1 and 2. Four penta-coordinate CuII atoms are located at the N 2 O 2 cavities of the ligand (L)4- units, two LaIII/CeIII atoms are surrounded by the open-chain 18-crown-6 (O 6) coordination environment. At the same time, eight bridged phenol oxygen atoms connect the six CuII/LnIII atoms. Infinite three-dimensional supra-molecular structures are formed in complexes 1 and 2 through H-bonds. The intermolecular interactions were quantitatively analyzed by Hirshfeld surfaces, as well as, fluorescence properties have also been studied. [ABSTRACT FROM AUTHOR]

Two phenoxo-bridged homopolynuclear Cu(II) bis(salamo) type complexes, 1 and 2 , have been successfully obtained and structurally characterized. The theoretical calculations and fluorescence properties were investigated in detail. [Display omitted] The dinuclear Cu(II) complex [Cu 2 (HL)Br 2 (MeOH)]·MeOH (1) and the tetranuclear Cu(II) complex [Cu 4 (L) 2 ](ClO 4) 2 ·2EtOH (2), based on a new bis(salamo) type ligand H 3 L, have been successfully self-assembled and structurally characterized by X-ray single crystal diffraction experiments. In complex 1 , the partially deprotonated ligand unit (HL)2– is coordinated with the Cu(II) ions. It is noteworthy that two bromine ions and one methanol molecule with balanced charges are involved in the coordination. Both central coordination Cu(II) ions are five-coordinated. Finally, complex 1 can form a two-dimensional planar network structure and a one-dimensional chain-like structure through intermolecular hydrogen bonds and C H π interactions, respectively. Meanwhile, complex 2 has a centrosymmetric structure with two phenolic oxygen atoms bridging two molecules of metallized ligand [Cu 2 (L)] units, where Cu1 is five-coordinated and Cu2 is four-coordinated. Thus, complex 2 forms a three-dimensional superamolecular network structure and a one-dimensional chain-like structure through intermolecular hydrogen bonds and π–π stacking interactions, respectively. The energy gaps between the HOMO and LUMO orbitals of complexes 1 and 2 were investigated by DFT calculations, indicating that the complexes are stable. The interaction sites of the ligand with the Cu2+ ions were examined by ESP investigation, and the results are consistent with the crystal structure. The weak intermolecular interaction forces of complexes 1 and 2 were explored by Hirshfeld surfaces and IRI analyses. The luminescent properties of complexes 1 and 2 were illustrated by fluorescence spectroscopy research. [ABSTRACT FROM AUTHOR]

• The pyridine-including half-salamo-like ligands HL1 and HL2 have been developed successfully. • Two first Co(III) complexes, [Co(L1)(N 3) 2 ] (1), and [Co(L2)(N 3) 2 ] (2) were synthesized and ascertained structurally. • The complexes 1 and 2 are unusual salamo-like Co(III) complexes with variable valence. This situation has never reported in the previous salamo-based complexes. Two structurally novel Co(III) complexes have been successfully constructed from the pyridine-including half-salamo-like ligands (HL1 and HL2), namely as [Co(L1)(N 3) 2 ] (1) and [Co(L2)(N 3) 2 ] (2). The structural features of complexes 1 and 2 have been confirmed by means of single crystal X-ray diffraction experiment. The structural studies revealed that complexes 1 and 2 have similar structures. The characterization of the two ligands and their Co(III) complexes was ascertained by means of infrared spectra, ultraviolet spectra and Hirshfeld surfaces analyses. In addition, compared with the ligands HL1 and HL2, the fluorescence intensities of the corresponding complexes 1 and 2 decreased significantly. When Co(II) salt was gradually added to the ligand solution, the intensity of the fluorescence emission peak decreased with the continuous addition of Co(II) salt until this trend stopped, which indicates that the introduction of Co(II) ion leads to the charge transfer from the ligand to Co(III) ion. Two structurally novel Co(III) complexes have been successfully constructed from the pyridine-including half-salamo-like ligands (HL1 and HL2), namely as [Co(L1)(N 3) 2 ] (1) and [Co(L2)(N 3) 2 ] (2). The characterization of the two ligands and their Co(III) complexes was ascertained by means of infrared spectra, ultraviolet spectra, X-ray crystallography, fluorescence spectra and Hirshfeld surfaces analyses. [Display omitted] [ABSTRACT FROM AUTHOR]

• A new kind of single‐armed salamo‐type ligand H 3 L and two corresponding Zn(II) complexes have been synthesized. • All of the Zn(Ⅱ) atoms in complexes 1 and 2 are penta-coordinated, highly distinct configurations are obtained because of the introduction of two kinds of counter-anions. • Fluorescence properties of H 3 L and complexes 1 and 2 were also investigated. Di- and tetra-nuclear Zn(II) complexes, [Zn 2 (L)(µ -OAc)(CH 3 OH)]·CH 3 OH (1) and [Zn 4 (L) 2 (OMe) 2 ]·2CH 3 COCH 3 ·CH 3 OH (2) have been successfully self-assembled by the reaction of a single‐armed salamo‐type ligand (H 3 L), Zn(OAc) 2 ·2H 2 O and Zn(NO 3) 2 ·6H 2 O, respectively. In the ligand H 3 L, tetradentate N 2 O 2 donor part of pocket I and NO 2 donor part of pocket II are designed to bond Zn(II) atoms, then unusually structural complexes were obtained by counteranion-driven self-assembled. Both complexes 1 and 2 are characterized by elemental analyses, IR spectra, UV-Vis spectra and single crystal X-ray diffraction. All of the Zn(II) atoms in complexes 1 and 2 are penta-coordinated, but highly distinct configurations are obtained because of the introduction of two kinds of counter-anions. In complex 1 , μ- OAc− counter-anion connects the two Zn(II) atoms in one ligand. In complex 2 , μ- OMe− counter-anions link the Zn(II) atoms within two ligand molecules and the structure of complex 2 is more complicated. What's more, in complex 1 , all Zn(II) atoms have the geometries of distorted trigonal bipyramid, while in complex 2 , all Zn(II) atoms have the geometries of distorted square pyramid. There are obvious π···π stacking interactions existing in complexes 1 and 2 , which are quantitatively valued by Hirshfeld surfaces analyses. Fluorescence properties are also investigated. Di- and tetra-nuclear Zn(II) complexes, [Zn 2 (L)(µ -OAc)(CH 3 OH)]·CH 3 OH (1) and [Zn 4 (L) 2 (OMe) 2 ]·2CH 3 COCH 3 ·CH 3 OH (2) have been successfully synthesized and structurally characterized. The fluorescence properties were also investigated. [Display omitted] [ABSTRACT FROM AUTHOR]

• A new heterobimetallic [Cu(II) 2 Pr(III)] complex with a symmetric flexible bis(salamo)-type ligand was synthesized and characterized structurally. • There are two different metal-binding sites of N 2 O 2 and O 6 (two being specific for the 3d metal ions and the other for the 4f metal ion) for the synthesis of heteropolynuclear 3d-4f complex with a flexible bis(salamo)‐type ligand. • Hirshfeld surface analysis and luminescence of the [Cu(II) 2 Pr(III)] complex was investigated. A new heterobimetallic 3d-4f [Cu(II) 2 Pr(III)] complex [Cu 2 Pr(L)(ƞ 2-NO 3) 3 (EtOH) 2 ]·2EtOH with a symmetric flexible bis(salamo)-type ligand, (1E,1′E)-2,3-dihydroxynaphthalene-1,4-dicarbaldehyde O,O -di(3-((((E)-3-ethoxy-2-hydroxybenzylidene)amino)oxy)propyl)dioxime (H 4 L), has been synthesized and characterized structurally. Single crystal X-ray diffraction analysis showed that the ligand was fasten by different metal ions to form a hetero-trinuclear complex with C-shaped structure, where two N 2 O 2 -donors of the completely deprotonated ligand (L)4− unit and two oxygen atoms from two ethanol molecules coordinate with Cu(II) atoms (Cu1, Cu2), respectively, to form two five-coordinated square pyramid geometries. Meanwhile, where the O 6 cavity coordination sphere of the ligand (L)4− unit and six oxygen atoms from three nitrate groups coordinate with the Pr(III) atom together to form a twelve-coordinated icosahedron. Due to the Cu(II) atom in the O 6 cavity was replaced by the Pr(III) atom, it shows that the hetero-trinuclear complex after self-assembly is more stable than the homo-trinuclear complex. At the same time, through UV–Vis titration spectrometric analysis, we can observed that the hetero-trinuclear [Cu(II) 2 Pr(III)] complex is obtained by 1 equiv. Pr(NO 3) 3 ·5H 2 O and 2 equiv. Cu(NO 3) 2 ·3H 2 O and 1 equiv. H 4 L. Significantly, fluorescence properties and Hirshfeld surfaces analyses of the [Cu(II) 2 Pr(III)] complex was also studied. A new heterobimetallic [Cu(II) 2 Pr(III)] complex with a symmetric flexible bis(salamo)-type ligand, (1E,1′E)-2,3-dihydroxynaphthalene-1,4-dicarbaldehyde O,O-di(3-((((E)-3-ethoxy-2-hydroxybenzylidene)amino)oxy)propyl)dioxime (H 4 L), has been synthesized and characterized structurally. Two five-coordinated Cu(II) atoms and one twelve-coordinated icosahedron Pr(III) atom are located in different coordination environments, respectively, fluorescence properties, Hirshfeld surfaces analyses and DFT calculations of the [Cu(II) 2 Pr(III)] complex was also studied. [Display omitted]. [ABSTRACT FROM AUTHOR]

• The first 3d-3d′ heterobimetallic [Cu(II) 2 Mn(II)] bis(salamo)-based complex was synthesized and characterized structurally. • The different natures of the N 2 O 2 and O 6 sites of H 4 L lead to the site‐selective introduction of two various metal(II) atoms. • Unusual fluorescence behavior of the [Cu(II) 2 Mn(II)] complex was reported. The first 3d-3d′ heterobimetallic [Cu(II) 2 Mn(II)] complex, [Cu 2 Mn(L)(µ 2 -NO 3) 2 ] was reported, and formed by an acyclic tricompartmental bis(salamo)-based ligand H 4 L and different metal salts. Its structure was characterized by physicochemical and spectroscopic methods. The ligand H 4 L has two identical N 2 O 2 sites and one O 6 site separated by phenoxy groups. Two penta-coordinate Cu(II) atoms and one octa-coordinated Mn(II) atom are located respectively in these two different coordination environments. Through the analysis of the Hirshfeld surfaces of the [Cu(II) 2 Mn(II)] complex, the intermolecular interactions involved in the crystal structure can be shown, and the corresponding quantitative information is given by fingerprint. The [Cu(II) 2 Mn(II)] complex units are combined by intermolecular C-H•••O hydrogen bonds to form a two-dimensional supramolecular structure. Unusual fluorescence behavior of the [Cu(II) 2 Mn(II)] complex was further studied. [Display omitted] [ABSTRACT FROM AUTHOR]

Three novel N 4 -cavity Cu(II), Ni(II) and Zn(II) complexes were successfully synthesized via the reactions of a novel pyridine-containing N 4 -cavity bisoxime ligand L. All three complexes are monoclinic systems. Complexes 2 and 3 form centrosymmetric helical molecules. Complexes 1 – 3 have been characterized by elemental analysis, IR, UV–Vis spectroscopy and single crystal X-ray crystallography. In addition, supramolecular interactions, Hirshfeld surface analysis to analyze the crystal properties have been studied. [Display omitted] • A novel ligand L with N4 cavity was synthesized and characterized. • Three excess metal single crystals were synthesized via the ligand L. • Hirshfeld surface analysis was performed on single crystals. Three novel N 4 -cavity Cu(II), Ni(II) and Zn(II) mononuclear complexes, [Cu(L)(NO 3) 2 ][Cu(L)(NO 3)]NO 3 (1) [Ni(L)(NO 3) 2 ] (2) and [Zn(L)(NO 3) 2 ] (3) were successfully synthesized via the reactions of a pyridine-containing N 4 -cavity bisoxime ligand L (L = 2,2′-[Ethylenedioxobis(azetidinyl)]pyridine) with Cu(II), Ni(II) and Zn(II) nitrates, respectively. Complexes 1 – 3 were characterized via elemental analysis, IR, UV–Vis spectra and X-ray crystallography. All three complexes are monoclinic systems, containing one M(II) atom and one (L) ligand moiety. Complexes 2 and 3 form centrosymmetric molecules. In addition, supramolecular interactions, Hirshfeld surface analysis were used to analyze the crystal properties that have been studied. [ABSTRACT FROM AUTHOR]

A new pyridine-decorated half-salamo-like ligand (HL) was designed and synthesized. Three novel anion-dependent Cu(II) complexes [Cu(L)Cl]·CH 3 OH (1), [Cu(L)Br] (2) and [Cu(L)(NO 3)] (3) have been synthesized and characterized structurally. Furthermore, DFT calculations were investigated in the complexes 1 , 2 and 3. Paradoxically, the fluorescence intensities of these Cu(II) complexes are significantly increased compared to the ligand. [Display omitted] • A new pyridine-decorated half-salamo-like ligand was synthesized. • Three anion-dependent Cu(II) complexes 1 , 2 and 3 have been synthesized and characterized structurally. • The fluorescence intensities of these Cu(II) complexes are significantly increased compared to the ligand. A new pyridine-decorated half-salamo-like ligand (HL) was designed and synthesized by a one-pot method. Based on this ligand, the single crystals of three anion-dependent Cu(II) complexes [Cu(L)Cl]·CH 3 OH (1), [Cu(L)Br] (2) and [Cu(L)(NO 3)] (3) have been cultivated successfully and the structural features were determined by single crystal X-ray diffraction analyses. The results showed that the complexes 1 , 2 and 3 have homologous mononuclear structures, in which the five-coordinated Cu(II) atom is not only surrounded by the N 3 O cavity of the ligand (L)- unit, but also coordinated with Cl−, Br− and NO 3 − as auxiliary coordination, respectively. The ligand HL and the complexes 1 , 2 and 3 were characterized via elemental analyses, IR and UV–Vis spectroscopy. The short-range interactions of the complexes 1 , 2 and 3 were investigated by Hirshfeld surfaces analyses. Furthermore, DFT calculations were investigated in the complexes 1 , 2 and 3. Paradoxically, the fluorescence intensities of these Cu(II) complexes are significantly increased compared to the ligand. [ABSTRACT FROM AUTHOR]

Three trinuclear complexes 1 - 3 possessed inversion centers have been successfully synthesized by wet-chemical method using asymmetric salamo-based polydentate chelating ligand (H 2 L) with Co(OAc) 2 ·4H 2 O and Ni(OAc) 2 ·4H 2 O, respectively. [Display omitted] Three trinuclear complexes, [{CoL(MeOH)(μ -OAc)} 2 Co] (1), [{CoL(EtOH)(μ -OAc)} 2 Co]·2CH 3 CH 2 OH (2) and [{NiL(MeOH)(μ -OAc)} 2 Ni]·2CH 3 OH (3) have been successfully synthesized by wet-chemical method using asymmetric salamo-based polydentate chelating ligand (H 2 L) with transition metal(II) acetate (Co(OAc) 2 ·4H 2 O or Ni(OAc) 2 ·4H 2 O). The ligand H 2 L with N 2 O 2 coordination cavity can accommodate transition metals, at the same time, the oxygen atoms of the phenolic hydroxyl groups can bridge the metal atoms to obtain muiltnuclear metal complexes. There are inversion centers in complexes 1 – 3 and all M(II) atoms possess six-coordinated distorted octahedral geometries. Complexes 1 and 3 are further assembled into extended two-dimensional supramolecular via intermolecular interactions, but complex 2 forms three-dimensional supramolecular structure. The interactions were quantitatively determined by Hirshfeld surfaces analyses. Significantly, complexes 1 – 3 have been characterized by elemental analyses, IR spectra, UV–Vis spectroscopy and X-ray crystallography analyses. Fluorescence properties were also investigated. [ABSTRACT FROM AUTHOR]

• A novel salamo-like ligand H 2 L containing double terminal pyridine groups was designed and synthesized. • The structurally different Co(II) MOF and Cd(II) coordination polymer were self-assembled successfully. • The N 2 O 2 cavity of the Cd(II) coordination polymer are not involved in the coordination, while those of the Co(II) MOF participate in the construction of metal organic framework. • Both Co(II) MOF and Cd(II) coordination polymer have good thermal stability. Two novel structurally characterized Co(II) metal-organic framework (Co(II) MOF) and Cd(II) coordination polymer (Cd(II) CP), [{Co(L)} 2 ] n ·nCH 3 COCH 3 and [Cd(H 2 L)(CH 3 COO) 2 ] n were self-assembled from a newly designed salamo-like ligand H 2 L bearing double terminal pyridine groups and Co(II) and Cd(II) ions, respectively. In the Co(II) MOF, the Co1 and Co2 ions are six-coordinated octahedron geometries, have similar coordination environments, and are located in the N 2 O 2 cavities of the ligand (L)2− units, forming "Co1-L" and "Co2-L" parts, respectively. The terminal pyridine N atoms of the "Co1-L" (or "Co2-L") part are connected with "Co1-L" and "Co2-L" parts respectively, forming a metal-organic framework with double helix structure in the a -direction and regular channels in the c -direction. In the Cd(II) CP, Cd(II) ion is seven-coordinated single cap triangular prism geometry, did not participate in the coordination of the N 2 O 2 cavity, but coordinated with free acetate in the solution. Two bidentate acetate anions chelate to Cd1 ion, and two Cd1 ions are bridged by O atom of one of the acetate anions to form Cd 2 (OAc) 2 unit which was used as the junction point to connect with the terminal pyridine N atoms of H 2 L. Finally, the coordination polymer with large pore channels was formed. Spectroscopic analyses of H 2 L and its Co(II) MOF and Cd(II) CP are performed using IR, UV–Vis and fluorescence spectroscopy. TGA analyses show that the Co(II) MOF and Cd(II) CP have good stabilities. Various short-range interactions in the Co(II) MOF and Cd(II) CP are investigated through Hirshfeld surfaces analyses. Image, graphical abstract [ABSTRACT FROM AUTHOR]

Three structurally different Cu(II), Co(II) and Ni(II) complexes constructed from a new single salamo-like ligand H 2 L and ancillary ligand 4,4′-bipy were synthesized and structurally characterized. [Display omitted] • A new single salamo-like ligand H 2 L has been designed and synthesized. • The obtained three Cu(II), Co(II) and Ni(II) complexes possess different structures. • Theoretical calculations (Hirshfeld surfaces and DFT) and fluorescence properties of the three complexes are investigated. A new salamo-based ligand H 2 L was designed and synthesized, and its structurally different Cu(II), Co(II) and Ni(II) complexes based on ancillary ligand 4,4′-bipy were obtained. The Cu(II) complex has a mononuclear structure with the molecular formula of [Cu(L)], while the Cu(II) ion adopts a twisted four-coordinate quadrilateral geometric configuration. One dimensional chain-like supramolecular structure is formed by intermolecular interactions. In the Co(II) complex, there is a dimer structure and the molecular formula is [Co 2 (L) 2 (4,4′-bipy)]. The Co(II) ions possess five-coordinated trigonometric bipyramid geometric configurations. A two-dimensional layered supramolecular structure is formed by intermolecular interactions. The Ni(II) complex has a one-dimensional polymer structure and its molecular formula is [Ni(L)(4,4′-bipy)] n ·nEtOH·nAce. The Ni(II) ions have six-coordinated octahedron geometric configurations. Through the intermolecular interactions, a three-dimensional supramolecular structure is formed. The ligand H 2 L and its three complexes were studied in detail by IR, UV–Vis and emissive spectra. The short-range interactions in the Cu(II), Co(II) and Ni(II) complexes were calculated by Hirshfeld surfaces analyses. The molecular orbital energy levels and molecular stability were analyzed by DFT calculations. [ABSTRACT FROM AUTHOR]

• Two multi-nuclear Ni(II)-based complexes have been successfully prepared by the complexation of more flexible salamo-type ligand (H 2 L) with nickel salts of different anions. • The structure of tetra-nuclear complex 2 is particularly unique because the flexibility of the ligand is better, which creates conditions for the intramolecular self-assembly. Two new tri- and tetra-nuclear Ni(II)-based complexes, [{NiL(EtOH)(μ -OAc)} 2 Ni]·4EtOH (1) and [Ni 4 L 2 (μ 3 -OMe) 4 (MeOH) 4 ] (2), supported by a more flexible salamo-type ligand H 2 L containing coumarin functional groups have been synthesized. Complex 1 is tri-nuclear, including three Ni(II) atoms with hexa-coordinated octahedral geometries. X-ray single-crystal structure analysis revealed that complex 2 is a novel tetra-nuclear structure previously unreported, and the geometry of four Ni(II) atoms with hexa-coordinate can be regarded as octahedron. Interestingly, due to the improvement of the flexibility of salamo-type ligand H 2 L, complex 2 is obtained by the form of intramolecular self-assembly. Moreover, the fluorescence properties of H 2 L and its Ni(II)-based complexes were studied. Subsequently, the supramolecular structure, Hirshfeld surfaces analyses and DFT calculations of the two Ni(II)-based complexes have been performed. Image, graphical abstract Two new tri- and tetra-nuclear Ni(II)-based complexes, [{NiL(EtOH)(μ -OAc)} 2 Ni]·4EtOH (1) and [Ni 4 L 2 (μ 3 -OMe) 4 (MeOH) 4 ] (2) , supported by a more flexible salamo-type ligand H 2 L containing coumarin functional groups have been synthesized and characterized structurally. Interestingly, complex 2 is a novel tetra-nuclear structure previously unreported. The fluorescence properties, Hirshfeld surfaces analyses and DFT calculations of H 2 L and its Ni(II)-based complexes were studied. [ABSTRACT FROM AUTHOR]

The Cu(II) and Ni(II) complexes self-assembled from a novel salamo-like ligand H 2 L containing double terminal pyridine groups, [Cu(LH)]NO 3 ⋅CH 3 CH 2 OH and [{Ni(L)} 2 ] n ·nC 5 H 5 N⋅nCH 3 COCH 3 were designed and synthesized. The Cu(II) atom is located at the N 2 O 2 cavity of the deprotonation ligand (L)2− moiety, but the N atoms of the terminal pyridine groups of the ligand (L)2− moiety is not involved in the coordination, and forms a four-coordinated twisted quadrilateral geometry. While the Ni(II) atom (Ni1 or Ni2) is sited in the N 2 O 2 cavity of the deprotonation ligand (L)2− moiety and forms a plane, the terminal pyridine N atoms from the two adjacent [Ni(L)] moieties also coordinated with the Ni(II) atom in the axial positions to form a slightly distorted octahedral geometry with six-coordination. The benzene and pyridine rings of the ligand (L)2− moiety are rotated and create an angle, result to form a chiral MOFs using an achiral ligand (L)2− moiety. • Containing double terminal pyridine groups novel salamo-like ligand was synthesized. • The structurally different Cu(II) and Ni(II) complexes were self-assembled. • The Cu(II) and Ni(II) complexes have huge structural differences. • Compared with the Cu(Ⅱ) complex, the Ni(Ⅱ) complex has better thermal stability. A novel structurally characterized salamo-like ligand H 2 L contained double terminal pyridine groups was designed and synthesized. The single crystals of the Cu(II) and Ni(II) complexes are grown up through coordination of H 2 L with Cu(II) and Ni(II) ions, respectively, determined as [Cu(LH)]NO 3 ⋅CH 3 CH 2 OH and [{Ni(L)} 2 ] n ·n3C 5 H 5 N·nCH 3 COCH 3. The Cu(II) atom is located at the N 2 O 2 cavity of the deprotonation ligand (L)2− moiety, but the N atoms of the terminal pyridine groups of the ligand (L)2− moiety is not involved in the coordination, and forms a four-coordinated twisted quadrilateral geometry. While the Ni(II) atom (Ni1 or Ni2) is sited in the N 2 O 2 cavity of the deprotonation ligand (L)2− moiety and forms a plane, the terminal pyridine N atoms from the two adjacent [Ni(L)] moieties also coordinated with the Ni(II) atom in the axial positions to form a slightly distorted octahedral geometry with six-coordination. In the formation of MOFs, the benzene and pyridine rings of the ligand (L)2− moiety are rotated and create an angle, result to form a chiral MOFs using an achiral ligand (L)2− moiety. View of MOFs in the C direction, the Ni(II) complex has four different size of apertures in its structure, and presences a large amount of protonic hydrogen. Spectroscopic analyses of H 2 L and its Cu(II) and Ni(II) complexes are performed using IR, UV–Vis and fluorescence spectroscopy. Compared with the Cu(II) complex, the Ni(II) complex has better thermal stability. The magnetic analyses were also carried out. Hirshfeld surfaces analyses are carried out to analyze various short-range interactions in H 2 L and its Cu(II) complex. [ABSTRACT FROM AUTHOR]

Three new multi-nuclear Cu(II) complexes have been successfully synthesized by the one-pot reaction of a bis(salamo)-based ligand H 3 L and different copper(II) salts and characterized structurally. • Three new multi-nuclear Cu(II) complexes have been successfully synthesized and characterized structurally. • Complex 3 is a novel penta-nuclear structure derived of the ligand (HL)2- units. • Effects of counteranions and fluorescence properties were also investigated. Three new multi-nuclear Cu(II) complexes, [Cu 4 (L) 2 (CH 3 OH) 2 ](NO 3) 2 ·2CH 3 OH (1), [Cu 4 (L) 2 (CH 3 OH)(CH 3 CN)](ClO 4) 2 ·2CH 3 OH (2) and [Cu 4 (HL) 2 (μ 2 -Cl) 2 Cl 2 (CH 3 CH 2 OH) 2 ][CuCl 2 ]·CHCl 3 (3) have been successfully synthesized by the one-pot reaction of a bis(salamo)-based ligand H 3 L with Cu(NO 3) 2 ·3H 2 O, Cu(ClO 4) 2 ·6H 2 O and CuCl 2 ·2H 2 O, respectively. Complexes 1 and 2 are monoclinic systems including four Cu(II) atoms with two completely deprotonated ligand (L)3- units, which form centrosymmetric helical molecules. Complex 3 is triclinic system including five Cu(II) atoms with two incompletely deprotonated ligand (HL)2- units, which forms an expanded structural molecule. Complexes 1 – 3 have been characterized by elemental analyses, IR, UV–Vis spectroscopy and single crystal X-ray crystallography. In addition, supramolecular interactions, Hirshfeld surfaces analyses, effects of counteranions and fluorescence properties were also investigated. [ABSTRACT FROM AUTHOR]

Three new complexes 1 – 3 coordinated to a more flexible salamo-based ligand have been successfully prepared and characterized structurally. The structure of the complex 3 is novel, and self-assemblied by a more flexible salamo-based ligand. • Three complexes have been successfully prepared. • These complexes have been characterized structurally. • Due to the flexibility of ligands, the structure of complex 3 is more unique. Three new multinuclear complexes, [{CoL(MeOH)(μ -OAc)} 2 Co]·6CH 3 OH (1) [{NiL(H 2 O)(μ -OAc)} 2 Ni]·6CH 3 OH·0.442H 2 O (2) and [{Zn 2 L 2 (μ -OH)} 2 ]·2NH(CH 2 CH 3) 3 ·4CH 3 OH·H 2 O (3) , based on a more flexible salamo-based ligand H 2 L containing coumarin functional groups have been synthesized and characterized structurally. The complex 1 is trinuclear, and all Co(II) atoms have octahedral geometries. A similar trinuclear complex 2 involving three Ni(II) atoms with hexa -coordinated octahedral geometries was obtained. For the complex 3 , it is a novel symmetric tetranuclear structure, and four Zn(II) atoms have penta -coordinated trigonal bipyramidal geometries. It is worth noting that the intramolecular self-assembly is achieved by changing the flexibility of salamo-based ligand in the complex 3. In addition, fluorescence titration experiments of the three complexes were carried out. The supramolecular structures of the three complexes were constructed via intermolecular hydrogen bond or π-π stacking interactions, and Hirshfeld surfaces analyses and DFT calculations were performed on the three complexes. [ABSTRACT FROM AUTHOR]

Two newly designed tetranuclear metal(II) complexes, [{Co(L)(μ -OAc)Co(CH 3 OH) 2 } 2 and [{Ni(L)(DMF)(μ -OAc)Ni} 2 derived from an unsymmetrical salamo-like ligand (H 3 L: 6-hydroxy-6′-methoxy-2, 2′-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol) were synthesized and characterized by elemental analyses, infrared spectroscopy, ultraviolet–visible absorption spectroscopy, fluorescence spectroscopy, X-ray single crystal diffraction and Hirshfeld surfaces analyses. • Tetranuclear Co(II) and Ni(II) complexes were synthesized and characterized structurally. • The crystal structures of Co(II) and Ni(II) complexes are very interesting. • Hirshfeld surfaces and fluorescent properties of the Co(II) and Ni(II) complexes were investigated. Two newly designed tetranuclear transition metal(II) complexes, [{Co(L)(μ -OAc)Co(CH 3 OH) 2 } 2 and [{Ni(L)(DMF)(μ -OAc)Ni} 2 derived from an unsymmetrical salamo-like donor-N 2 O 4 ligand (H 3 L: 6-hydroxy-6′-methoxy-2, 2′-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol) were synthesized and characterized by elemental analysis, FT-IR, UV-vis, fluorescence spectroscopy, X-ray crystallography and Hirshfeld surface analysis. The Co(II) complex includes two fully deprotonated (L)3− moieties, two μ-acetato ligands and four coordinated methanol molecules, bearing a highly symmetrical tetranuclear structure. The terminal Co(II) ions are penta-coordinated and have slightly twisted triangular bipyramidal geometries, and the central Co(II) ions are hexa-coordinated and possess slightly twisted octahedral geometries. The Co(II) complex was self-assembled by adequate intermolecular hydrogen bonding interactions giving rise to an infinite two-dimensional supramolecular structure. The Ni(II) complex adopts a symmetric tetranuclear structure including two fully deprotonated (L)3− units, two coordinated DMF molecules, and two μ-acetato ligands. All the Ni(II) ions are hexa-coordinated and have slightly twisted octahedral geometries. At the same time, the fluorescent properties and Hirshfeld surfaces analyses of the Co(II) and Ni(II) complexes were also investigated in detail. [ABSTRACT FROM AUTHOR]

A new naphthalenediol-based bis(salamo)-type fluorescent probe H 4 L for Zn2+ and CN− was reported. Probe H 4 L showed a highly selective fluorescence enhancement toward Zn2+ over other metal ions including Cd2+, and obtained the L-Zn 2+ complex can only detect CN− in various anions. Their recognition mechanisms were explained by Job plots, fluorescent and UV–vis titrations, and theoretical calculations. The L-Zn 2+ complex has been synthesized and structurally characterized using Hirshfeld surface analysis, elemental analyses, IR, UV–Vis and fluorescent spectra. Additionally, the relay probe with the wide adaptability of pH range and excellent stability showed highly selectivity for CN− recognition. A new naphthalenediol-based bis(salamo)-type fluorescent probe H 4 L was reported, H 4 L showed a highly selective fluorescence enhancement toward Zn2+ over other metal ions including Cd2+, and obtained the L-Zn 2+ complex can only detect CN− in various anions. Unlabelled Image • A highly selective and sensitive fluorescent probe H 4 L for Zn2+ and CN− was synthesized. • The L-Zn 2+ complex has been synthesized and characterized structurally. • Recognition mechanism for Zn2+ was supported by theoretical calculations. [ABSTRACT FROM AUTHOR]